Adducts of benzoquinonedimines



ADDUCTS OF BENZOQUINONEDIHVIINES Joseph E. Dunbar, Midland, Mich,assignor to The Dow Chemical Company, Midland, Mich, a corporation ofDelaware No Drawing. Filed Oct. 28, 1959, Ser. No. 849,162

Claims. (Cl. 2'60461) This invention is directed to the cyclopentadieneadducts of benzoquinonediimine compounds and corresponds to the formula.

In this and succeeding formulas, each R and R represents a lower alkylgroup containing from 1 to 4 carbon atoms, inclusive.

The compounds of this invention are white crystalline, solids, which aresoluble in many organic solvents such as diethyl ether, benzene andethanol. The compounds are of low solubility in water. The new compoundsare useful as parasiticides and are particularly adapted to be employedas toxic constituents of compositions for the control of bacteria andfungi.

The condensation products of the present invention may readily beprepared in a Diels-Alder condensation reaction by mixing togethercyclopentadiene with an N,N'-bis alkoxyphosphinothioyl)-p-benzoquinonediimine compound having the formula The oyclopentadieneand benzoquinonediimine compounds are preferably mixed together in aninert solvent as reaction medium. Suitable solvents include chloroform,benzene, toluene, and xylene. Under these conditions, the reactiontemperatures may vary over a wide range, as the reaction takes placesmoothly when the reactants are combined at any temperature in the rangeof from 0 C. to the boiling temperature of the reaction mixture or, in apressure-sealed reaction vessel, to 150 C., with the production of thedesired product. The reaction is conveniently carried out at roomtemperature. Good results are obtained when cyclopentadiene is employedin excess on a molar basis with respect to the benzoquinonediiminereactant.

In carrying out the reaction, the benzoquinonediimine reactant isdissolved in the reaction solvent, and to the resulting solution freshlyprepared cyclopentadiene is added with stirring. Stirring is thereaftercontinued and the reaction mixture maintained at a reaction temperaturefor a period of from 5 seconds to 7 days to obtain the desired N,N' bisalkoxyphos hinothioyl) -p-benzoquinone diinune-cyclopentadiene adduct.The latter is then recovered from the reaction mixture as residue byvaporizing off the solvent. The crude product may be recrystallized fromsolvents such as chloroform, carbon tetrachloride, ethyl acetate orcyclohexane.

The following examples illustrate the invention but are not to beconstrued as limiting.

Example 1.0,0,0',O-tetramethyl (1 4-dihydro-L4- methane-5,8-naphthylene)bis(ph0sphoramidothioate) S (CHzOhP-NH 13.2 grams (0.200 mole) offreshly prepared cyclopentadiene was added to a solution of 10.7 grams(0.0303

mole) of N,N'-bis(dimethoxyphosphinothioyl)-p-benzoquinone-diimine inmilliliters of chloroform and the resulting mixture allowed to stand atroom temperature for 42 hours. At the end of this period, the reactionmixture was brought to the boiling temperature and the hot solutiondecolorized with activated charcoal. The decolorized solution was thenevaporated to dryness to obtain as residue an 0,0,0,O-tetramethyl(1,4-dihydrol,4-methano-5 S-naphthylene) bis( phosphoramidothioate)product as a crystalline solid. The latter was purified byrecrystallizing successively from ethanol, glacial acetic acid andethanol to obtain a purified product melting at 165.5" C.

Example 2.-0,0,0,O' tetraeihyl (1,4 dilzya'ro 1,4-

methano-5,8-naph thylene) bis(phosphoramidothioate) 13 grams (0.20 mole)of freshly distilled cyclopentadiene is added to a solution of 12 grams(0.030 mole) of N,N-bis(diethoxyphosphinothioyl)-p-benzoquinonediiminein 100 milliliters of chloroform and the resulting mixture allowed tostand at room temperature for several days. The reaction mixture is thenheated to the boiling temperature, decolorized with activated charcoaland the decolorized solution is evaporated to dryness to obtain asresidue an 0,0,0',O'-tetraethyl (l,4-dihydro-l,4-meth ano 5,8naphthylene)-bis(phosphoramidothioate) product having a molecular weightof 476.

Example 3.O,0,0',O'-tetrais0propyl (1 441 ihydro-I ,1;- methan0-5,8-naphthylene) bis phosphoram i doth ioate) In a manner similar to thatpreviously described, 13 grams (0.20 mole) of cyclopentadiene and 14.0grams (0.030 mole) of N,N'-bis(diisopropoxyphosphinothioyl)-p-benzoquinonediimine are reacted in chloroform solvent to obtain thedesired 0,0,0,O-tetraisopropyl (1,4-dihydrol ,4-methano-5,S-naphthylene)-bis (phosphoramidothioate) having a molecular weight of 532.

Example 4.-0,0,0',O-tetra(normal-butyl) (I,/,-dihydro 1,4 methano 5,8naphthylene) bis(plz0sph0ramidothioate) In a similar manner, 13 grams(0.20 mole) of cyclopentadiene and 16 grams (0.03 mole) of N,N'-bis(dinormal butoxyphosphinothioyl) -p-benzoquinonediimine are reacted togetherin chloroform solvent to obtain the desired 0,0,0,O'-tetra(normal-butyl)(l,4-dihydro-l,4-

methano 5,8 naphthylene)-bis(phosphoramidothioate) product having amolecular weight of 588.

Example ano-S,S-naphthylene)bis(phosphoramidothioate) by the reaction ofN,N'-bis(di-normal-propoxyphosphinothioyl)- p-benzoquinonediimine withcyclopentadiene.

The compounds of the present invention have been found to be useful astoxic components in parasiticidal compositions. For such use theproducts may be dispersed on inert, finely divided solids and employedas dusts or may be dispersed in water with wetting agents and theresulting dispersions employed as sprays. In other operations, theproducts may be employed as constituents in emulsions or dispersionswith or without the addition of wetting, dispersing or emulsifyingagents. These compounds are particularly useful for the control of plantpathogens such as the causative organism of wheat rust disease (Pucciniagraminis-tritici) and the causative organism'of tomato early blight(Alternaria solani).

- In a representative operation of its use as an agent for the controlof plant pathogens, good controls of wheat rust disease were obtainedwhen wheat plants susceptible A one-diimines employed, as startingmaterials in accordance with the teachings of the present inventionmaybe prepared by (1) mixing together about 2 molar proportions of asuitable 0,0'-dialkylphosphorochloridothioate with 1 molar proportion ofphenylenediimine in the presence of about 2 molar proportions of anagent such as alkali metal hydroxide in an inert organic solvent at atemperature of from 0 to 90 C. to produce an intermediate0,0,0,O',-tetraalkyl-p-phenylene bis(phosphoramidothiioate) and v(2)reacting the intermediate thus prepared with slight excess on a molarbasis of lead tetraacetate in an inert organic solvent such as benzene,chloroform, toluene or xylene inthe temperature range of from 10 to 50C. to produce the desired N,N'-bis to said disease were sprayed with anaqueous dispersion containing 05 pounds of 0,0,0',O',-tetramethyl (1,4-dihydro-.1,4Fmethanoi-5,8-lnaphthylene) l'bisl (phosphoramidothioate) in100 gallons of spray medium and thereafter inoculated with the rustfungus organism, Puccinia graminis-tritici..

' I'he N,=N'bis(dialkoxyphosphinothioyl) wp-benzoquin- (dialkoxyphophinothioyl) p-benzoquinonediimine and lead salt by-produ'ct,removing the latter by filtration and recovering the desired diiminereactant by conventional procedures.

I claim: a i

1. A cyclopentadiene adduct of N,Nbis-(dialkoxyph;sphinothioyl)-p-benzoquinonediimine having the for mu a wherein R and Reach represent a lower alkyl radical containing from 1 to 4 carbonatoms, inclusive.

2. 0,0,0, -tetramethyl (1,4 dihydro l,4methano- 5,8-naphthylene)bis(phosphoramidothioate) 3. 0,0,0,O'-tetraethyl(l,4-dihydro-.l,4-methano-5,8 naphthylene) bis (phosphoramidothioate) 4.0,0,0',O',-tetraisopropyl (1,4-dihydro-1,4-methano S, S-naphthylene) bis(phosphoramidothio a-te) 5. O,Q,0,O' tetra (normal-butyl) (1,4dihydro-1,4,-

methano-5,8-naphthylene )bis(phosphoramidothioate) No references cited.

1. A CYCLOPENTADIENE ADDUCT OFN,N''BIS(DIALKOXYPHOSPHINOTHIOYL)-P-BENZOQUINONEDIIMINE HAVING THEFORMULA